Process for treating petroleum emulsions



"Patented Mg. 17, race.

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ST.'.I|OUIS, MISSOURI, ASSIGNOR TO WM. S. BARNICKEL 8c MISSOURI, A. CORPORATION Ola? MISSOURI.

Y PROCESS FOR TREATING lPETB/OLEUM EMULSIONS.

of water distributed throughout the body of 'oil and constituting the dispersed phase of the emulsion and films of matter that encase the droplets of water. They are obtained from producing'wells and from the bottom of oil storage tanks and are commonly referred to as cut oil, roily'oil, emulsifiedoil and bottom settlings.

The object of my present invention is to provide a novel and inexpensive process for separating emulsions of the character referred to into their component parts of oil and water or brine.

Briefly described, my process consists in subjecting a petroleum emulsion to the action of a treating agent consisting of an ester of a naphthenic acid, in such a manner that the emulsion will break and separate into its component parts of oil and water or acids were first obtained from soaps,

brine when the emulsion is permitted to remain in aquiescent state after treatment.

In order to give a clear understanding of the esters contemplated" 'by my process, I

will point out somev of the characteristics of the naphthenes from which said esters'are obtained. Naphthenes are hydrocarbons of the C l-T series which belong, not to the ethylene group, but 'to What is known as the naphthene or C fi kfl group. They are found in most oils and closely resemble the parafines. Related to the naphthenes are naphthenic acids. These naphthenic salted out -of the alkaline sludge obtained in the refining of illuminating oil. Said isolated acids belong to the series (LE O, and

'difier somewhat intheir properties from the unsaturated acids derived from the series of they closely resembleon account. of their weak acid character. It has generally been accepted that they are mono-carbraylic' derivatives of. the naphthenes.

The naphthenes above referred to are capable of sulphonation, and whensubjected to such action, there results therefrom a na hthene, sulphonic acid of the formula C SO H. Due to the acidic character naphthenic acids may vary in their bility in oil and in other solvents.

ethyl alcohol, iso-propyl 7, 1925. Serial No. 61,135.

of this material it is frequently referred to as naphthenic acid, although it should be more properly called naphthene, sulphonic acid. Petroleum sludges may also contain .a true naphthenic sulphonic acid such as the series C H HSO .O It is some" what difficult to isolate these acids fret-n. each other. Generally speaking, the sulphonated naphthene acids are produced in the refining of petroleum, and subsequertly are subjected to hydrolysis to give the naphthenic acids. -Usually, the method of hydrolysis is not complete and there always remain some sulphonated naphthene acids. On the other hand, in the actual refining process of washing with sulphuric acid-there may be present in the sludge some rnsul phonated naphthenic" acid. It will thus be seen that it is almost impossible to obtain a sulphonated, naphthenic acid in the absolute absence of the unsulphonated product, and consequently, the substance commonly referred to as naphthenic acid is essentially a mixture of the three series above referred to. I

Hereafter I shall refer to the above mentioned mixture as naphthenic acids and shall refer to those specific acids which contain a'sulphonic group or groups as sul- Y phonated, naphthenic acids. It is a matter of common knowledge that sulphonated,

acteristics, such as molecular weights, odor, color, their solubility in water and their solu- However, they are of commercial value and are used extensively in industrial processes, such as fat splitting agents and in the production of detergents.

has been described in the following U. S. patents: Nos. 1,233,700; 1,299,385; 1,319,027 1,396,399; 1,474 933; 1,493,111.

Esters capable of being used with my process can be obtained from naphthenic acids by combination with hydroxylated materials not derived from petroleum, such as aliphatic alcohols, including methyl alcohol,

alcohol and isobutyl alcohol, and from aromatic bodies, such as phenol, cresol, naphthol, etc. The method ofproduoing such known and consists in intimately mixing the acid containing material, such as naphthenic substances is WEll char- 7 The art of recovering these -materials or their salts is Well known and acid, with a molecular proportion of the nydroxyl-contaimng body, "and subjecting the mixture .to the action of a dehydrating age'nt,.sucl1- as sulphuric acid; The

, drogen of-either the carbonyl or of'thesul: ghonitl: group may be combined with the hyro Ijfiracusing my process a tr the kind above described,

a naphthenic acid," is brought into contact treating agent into a well in. which a petroleum emulsion is being produced; introducing. the treating agent into troducin gthe treating agent into a: tankin which a petroleum emulsion is 'sto-red' or introducing the treating agentinto a container that holds a sludge obtained from the bottom ;of an oil storagetanl r. The treating agentcan' also be introduced Into a producing" wellin way that it will become mixed with such a water and oil that are emerging from the ground before said water and oil enter the barrel of the well: pump or the tubin up 15 through which said water-and oil flow' to the surface of the ground; After treatment the emulsionis allo wed to standwin a quiescent state at a-suitable mit the water or brine to separate from the oil,-'or it maybe passed through a variety of apparatus, such as hay tan-ks, gun bar rels,- eta, such'as are now commonly used in acid hyeating agent of 4 namely, an ester of with an emulsion either "by-introducing the a conduit through which a petroleum emulsion is -flowing; in-- sisting of an ester of'a themc acid.

temperatureso as to per-- meats? L-clan'n as new and desire to secure by Let x ters Patent is:

1.- A process fortreating petroleum emuisions, characterized by subjecting the emulsion' to the action of a treating agent con slst ng of an ester of a 'naphthenic acid.

2; A process-for treating petroleum emul-- I si'ons, characterized a by subjecting theemulsion to the action of a-treatmg-agent'con- 3. A'process for-treating Petroleum emul sion to the action ofa treatingjagent con sisting of an aromatic ester of a-naphthenic aci i a 4. A process for treatingpetroleum-emulsions, characterized by'subjecti-n'g theIemuL sion toth'e'action-of-a treating agent consistacid.

5. A process for treating -petroleum emuls1ons,' characterized bysubjecting the'emuI- 60 I {anem a-DE GRdO-TE."

.s ulphonate'd naph-' si'ons, cha racterigedby subjecting the emul- 5 -mg of a mono-cyclic ester of a naphthenic" 

